Water-soluble granules of phthalocyanine compounds

ABSTRACT

Water-soluble granules of phthalocyanine compounds comprisinga) from 2 to 50% by weight of a water-soluble phthalocyanine compound,b) from 10 to 95% by weight of an anionic dispersing agent,c) from 0 to 25% by weight of a water-soluble organic polymer,d) from 0 to 10% by weight of a further additive ande) from 3 to 15% by weight of water, based on the total weight of the granules, are described.The granules are suitable especially as additives to washing agents for textile materials.

The present invention relates to water-soluble granules ofphthalocyanine compounds, to a method of producing them, and to the usethereof in washing agent preparations.

Water-soluble phthalocyanine dyes, especially zinc and aluminumphthalocyanine-sulfonates, are frequently used as photoactivators inwashing agent preparations. In view of the fact that suchphotoactivators dissolve too slowly in water, problems often arise,especially when there is inadequate mixing of the washing liquor,because the coloured photoactivators stain the laundry.

Solid microcapsules of phthalocyanine photoactivators that contain atleast 38% of an encapsulating material have already been described inEP-B-0 333 270, but those microcapsules are also not able to satisfy allof the consumer's requirements in terms of dissolving behaviour andstaining of the laundry.

It has now been found that, surprisingly, granules comprising awater-soluble phthalocyanine compound, an anionic dispersing agent and amaximum of 25% by weight of an organic polymer are distinguished by ahigh rate of dissolution in water, with the result that the problemsmentioned above are substantially or entirely eliminated. A furtheradvantage of such granules is that, even in the case of prolongedcontact with a non-ionic surfactant, the phthalocyanine compound is notdissolved out of the granules and the laundry is not stained.

The present invention accordingly relates to water-soluble granules ofphthalocyanine compounds comprising

a) from 2 to 50% by weight of a water-soluble phthalocyanine compound,

b) from 10 to 95% by weight of an anionic dispersing agent,

c) from 0 to 25% by weight of a water-soluble organic polymer,

d) from 0 to 10% by weight of a further additive and

e) from 3 to 15% by weight of water, based on the total weight of thegranules.

There come into consideration as the phthalocyanine compound for thegranules according to the invention phthalocyanine complexes having adi-, tri- or tetra-valent metal (complexes having a d⁰ or d¹⁰configuration) as the central atom. Such complexes are especiallywater-soluble Zn, Fe(II), Ca, Mg, Na, K, Al, Si(IV), P(V), Ti(IV),Ge(IV), Cr(VI), Ga(III), Zr(IV), In(III), Sn(IV) and Hf(VI)phthalocyanines, aluminum phthalocyanine and zinc phthalocyanine beingespecially preferred.

Advantageously, the composition according to the invention comprises aphthalocyanine compound of formula

[Me]_(q)—[PCQ₁]_(r) ⁻A_(s) ⁻  (1a)

or

[Me_(q)PCQ₂]_(r)  (1b)

wherein

PC is the phthalocyanine ring system;

Me is Zn, Fe(II), Ca, Mg, Na, K, Al—Z₁, Si(IV), P(V), Ti(IV), Ge(IV),Cr(VI), Ga(III), Zr(IV), In(III), Sn(IV) or Hf(VI);

Z₁ is a halide, sulfate, nitrate, acetate or hydroxy ion;

q is 0, 1 or 2;

r is from 1 to 4;

Q₁ is a sulfo or carboxyl group; or a radical of the formula

—SO₂X₂—R₆—X₃ ⁺; —O—R₆—X₃ ⁺; or —(CH₂)_(t)—Y₁ ⁺;

wherein

R₆ is branched or unbranched C₁-C₈alkylene; or 1,3- or 1,4-phenylene;

X₂ is —NH—; or —N—C₁—C₅alkyl-;

X₃ ⁺ is a group of the formula

and, in the case where R₆=C₁-C₈alkylene, may also be a group of theformula

Y₁ ⁺ is a group of the formula

t is 0 or 1;

and in the above formulae

R₇ and R₈ are each independently of the other C₁-C₆alkyl;

R₉ is C₁-C₆alkyl; C₅-C₇cycloalkyl; or NR₁₁R₁₂;

R₁₀ and R₁₁ are each independently of the other C₁-C₅alkyl;

R₁₂ and R₁₃ are each independently of the other hydrogen or C₁-C₅alkyl;

R₁₄ and R₁₅ are each independently of the other unsubstituted C₁-C₆alkylor C₁-C₆alkyl substituted by hydroxy, cyano, carboxy,C₁-C₆alkoxycarbonyl, C₁-C₆alkoxy, phenyl, naphthyl or by pyridyl;

u is from 1 to 6;

A₁ is the balance of an aromatic 5- to 7-membered nitrogen heterocyclewhich may contain one or two further nitrogen atoms as ring members, and

B₁ is the balance of a saturated 5- to 7-meambered nitrogen heterocyclewhich may contain 1 or 2 further nitrogen, oxygen and/or sulfur atoms asring members;

Q₂ is hydroxy; C₁-C₂₂alkyl; branched C₄-C₂₂alkyl; C₂-C₂₂alkenyl;branched C₄-C₂₂alkenyl or a mixture thereof; C₁-C₂₂alkoxy; a sulfo orcarboxyl radical; a radical of the formula

a branched alkoxy radical of the formula

or

an alkylethyleneoxy unit of the formula—(T₁)_(d)—(CH₂)_(b)(OCH₂CH₂)_(a)—B₃ or an ester of the formula COOR₂₃,in which formulae

B₂ is hydrogen; hydroxy; C₁-C₃₀alkyl; C₁-C₃₀alkoxy; —CO₂H; —CH₂COOH; SO₃⁻M₁ ⁺;

—OSO₃ ⁻M₁ ⁺; —PO₃ ²⁻; M₁; —OPO₃ ²⁻M₁; or a mixture thereof;

B₃ is hydrogen; hydroxy; —COOH; —SO₃ ⁻M₁ ⁺; —OSO₃ ⁻M₁ ⁺; or C₁-C₆alkoxy;

M₁ is a water-soluble cation;

T₁ is —O—; or —NH—;

X₁ and X₄ are each independently of the other —O—; —NH—; or—N—C₁-C₅alkyl;

R₁₆ and R₁₇ are each independently of the other hydrogen, a sulfo groupor a salt thereof, a carboxyl group or a salt thereof, or a hydroxylgroup, at least one of the radicals R₁₆ and R₁₇ being a sulfo orcarboxyl group or a salt thereof,

Y₂ is —O—, —S—, —NH— or —N—C₁-C₅alkyl;

R₁₈ and R₁₉ are each independently of the other hydrogen, C₁-C₆alkyl,hydroxy-C₁-C₆alkyl, cyano-C₁-C₆alkyl, sulfo-C₁-C₆alkyl, carboxy orhalo-C₁-C₆alkyl; unsubstituted phenyl; or phenyl substituted by halogen,C₁-C₄alkyl or C₁-C₄alkoxy, sulfo or by carboxy; or R₁₈ and R₁₉, togetherwith the nitrogen atom to which they are bonded, form a saturated 5- or6-membered heterocyclic ring that may in addition contain a furthernitrogen atom or an oxygen atom as ring member;

R₂₀ and R₂₁ are each independently of the other a C₁-C₆alkyl oraryl-C₁-C₆alkyl radical;

R₂₂ is hydrogen; unsubstituted C₁-C₆alkyl; or C₁-C₆alkyl substituted byhalogen, hydroxy, cyano, phenyl, carboxy, C₁-C₆alkoxycarbonyl or byC₁-C₆alkoxy;

R₂₃ is C₁-C₂₂alkyl, branched C₄-C₂₂alkyl, C₁-C₂₂alkenyl or branchedC₄-C₂₂alkenyl; C₃-C₂₂-glycol; C₁-C₂₂alkoxy; branched C₄-C₂₂alkoxy; or amixture thereof;

M is hydrogen; or an alkali metal ion or ammonium ion;

Z₂ is a chlorine, bromine, alkyl sulfate or aralkyl sulfate ion;

a is 0 or 1;

b is from 0 to 6;

c is from 0 to 100;

d is 0; or 1;

e is from 0 to 22;

v is an integer from 2 to 12;

w is 0 or 1; and

A is an organic or inorganic anion,

and

s in the case of monovalent anions A⁻ is equal to r and in the case ofpolyvalent anions is ≦r, it being necessary for A_(s) ⁻ to balance thepositive charge; and when r≠1, the radicals Q₁ may be identical ordifferent,

and wherein the phthalocyanine ring system may also comprise furthersolubilising groups.

The number of substituents Q₁ and Q₂ in formula (1a) and in formula(1b), respectively, which substituents may be identical or different, isfrom 1 to 8 and, as is customary with phthalocyanines, the number neednot be a whole number (degree of substitution). If other, non-cationicsubstituents are also present, the sum of the latter and the cationicsubstituents is from 1 to 4. The minimum number of substituents thathave to be present in the molecule is governed by the water-solubilityof the resulting molecule. An adequate solubility is achieved when theamount of phthalocyanine compound that dissolves is sufficient to causea photodynamically catalysed oxidation on the fibres. A solubility of aslow as 0.01 mg/l may be sufficient, but generally a solubility of from0.001 to 1 g/l is expedient.

Halogen is fluorine, bromine or, especially, chlorine.

There come into consideration as

groups especially:

The group

is preferred.

The above-listed groups likewise come into consideration as heterocyclicrings in the group

only the bond to the remaining substituents being effected by way of acarbon atom.

In all substituents, phenyl, naphthyl and aromatic hetero rings may besubstituted by one or two further radicals, for example by C₁-C₆alkyl,C₁-C₆alkoxy, halogen, carboxy, C₁-C₆alkoxy-carbonyl, hydroxy, amino,cyano, sulfo, sulfonamido etc.

A substituent from the group C₁-C₆alkyl, C₁-C₆alkoxy, halogen, carboxy,C₁-C₆alkoxycarbonyl and hydroxy is preferred.

There come into consideration as the

group especially:

All of the above-mentioned nitrogen heterocycles may in addition besubstituted by alkyl groups, either at a carbon atom or at a furthernitrogen atom located in the ring, in which case the methyl group ispreferred as alkyl group.

A_(s) ⁻ in formula (1a) denotes, as counterion to the positive charge ofthe remainder of the molecule, any desired anion. It is generallyintroduced by the preparation process (quaternisation), in which case itis preferably a halogen ion, an alkyl sulfate ion or an aryl sulfateion. Among the aryl sulfate ions mention should be made of thephenylsulfonate, p-tolylsulfonate and p-chlorophenylsulfonate ions. Itis also possible, however, for any other anion to function as the anion,since the anions can readily be interchanged in known manner; A_(s) ⁻mayalso be a sulfate, sulfite, carbonate, phosphate, nitrate, acetate,oxalate, citrate or lactate ion or another anion of an organiccarboxylic acid. In the case of mono-valent anions, the index s is equalto r. In the case of polyvalent anions, s assumes a value ≦r, butdepending on the conditions must be such that it exactly balances thepositive charge of the remainder of the molecule.

C₁-C₆Alkyl and C₁-C₆alkoxy are straight-chain or branched alkyl andalkoxy radicals, respectively, such as, for example, methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl,tert-amyl or hexyl and methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,sec-butoxy, tert-butoxy, amyloxy, isoamyloxy, tert-amyloxy or hexyloxy,respectively.

C₂-C₂₂Alkenyl is, for example, allyl, methallyl, isopropenyl, 2-butenyl,3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methylbut-2-enyl,n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl orn-octadec-4-enyl.

Preferred phthalocyanine compounds of formula (1a) for the granulesaccording to the invention correspond to formula

wherein

Me, q, PC, X₂, X₃ and R₆ are as defined for formula (1a);

M is hydrogen, or an alkali metal, ammonium or amine salt ion;

and the sum of the numbers r₁ and r₂ is from 1 to 4, and

A_(s) ⁻ exactly balances the positive charge of the remainder of themolecule, and correspond especially to formula

[Me]_(q)—[PC]—[SO₂NHR₆′—X₃′⁺A′⁻]_(r)  (3)

wherein

Me, q and PC are as defined for formula (1a);

R₆′ is C₂-C₆alkylene;

r₁ is a number from 1 to 4;

X₃′ is a group of the formula

or

in which formulae

R₇ and R₈ are each independently of the other unsubstituted C₁-C₄alkylor C₁-C₄alkyl substituted by hydroxy, cyano, halogen or by phenyl;

R₉ is R₇; cyclohexyl or amino;

R₁₁ is C₁-C₄alkyl;

R₂₁ is C₁-C₄alkyl; C₁-C₄alkoxy; halogen, carboxy, C₁-C₄alkoxycarbonyl orhydroxy; and

A′ is a halide, alkyl sulfate or aryl sulfate ion;

wherein the radicals —SO₂NHR′₆—X₃′⁺A⁻ may be identical or different.

Further phthalocyanine compounds that can be used in accordance with theinvention correspond to formula

 [Me_(q)PCSO₃—Y₃′]_(r)  (4)

wherein

PC is the phthalocyanine ring system;

Me is Zn, Fe(II), Ca, Mg, Na, K, Al—Z₁, Si(IV), P(V), Ti(IV), Ge(IV),Cr(VI), Ga(III), Zr(IV), In(III), Sn(IV) or Hf(VI);

Z₁ is a halide, sulfate, nitrate, acetate or hydroxy ion;

q is 0; 1; or 2;

Y₃′ is hydrogen, an alkali metal ion or an ammonium ion; and

r is any number from 1 to 4.

Special preference is given to those phthalocyanine compounds of formula(4) wherein

Me is Zn or Al—Z₁; and

Z₁ is a halide, sulfate, nitrate, acetate or hydroxy ion.

Further phthalocyanine compounds of interest that can be used inaccordance with the invention correspond to formula

wherein

PC, Me and q are as defined for formula (4);

R₁₇′ and R₁₈ ′ are each independently of the other hydrogen, phenyl,sulfophenyl, carboxyphenyl, C₁-C₆alkyl, hydroxy-C₁-C₆alkyl,cyano-C₁-C₆alkyl, sulfo-C₁-C₆alkyl, carboxy-C₁-C₆alkyl orhalo-C₁-C₆alkyl or, together with the nitrogen atom, form a morpholinering;

q′ is an integer from 2 to 6; and

r is a number from 1 to 4;

wherein, when r>1, the radicals

present in the molecule may be identical or different.

Further phthalocyanine compounds of interest that can be used inaccordance with the invention correspond to formula

wherein

PC, Me and q are as defined for formula (4);

Y′₃ is hydrogen, an alkali metal ion or an ammonium ion;

q′ is an integer from 2 to 6;

R₁₇ ′ and R₁₈ ′ are each independently of the other hydrogen, phenyl,sulfophenyl, carboxyphenyl, C₁-C₆alkyl, hydroxy-C₁-C₆alkyl,cyano-C₁-C₆alkyl, sulfo-C₁-C₆alkyl, carboxy-C₁-C₆alkyl orhalo-C₁-C₆alkyl or, together with the nitrogen atom, form a morpholinering,

m′ is 0 or 1; and

r and r₁ are each independently of the other any number from 0.5 to 3.5,the sum r+r₁ being a minimum of 1 and a maximum of 4.

Where the central atom Me in the phthalocyranine ring is Si(IV), thephthalocyanines used in accordance with the invention may contain, inaddition to the substituents on the phenyl nucleus of the phthalocyaninering, also axial substituents (=R₂₄). Such phthalocyanines correspond,for example, to formula

wherein

R₂₄ is hydroxy; C₁-C₂₂alkyl; branched C₄-C₂₂alkyl; C₁-C₂₂alkenyl;branched C₄-C₂₂alkenyl or a mixture thereof; C₁-C₂₂alkoxy; a sulfo orcarboxyl radical, a radical of the formula

a branched alkoxy radical of the formula

or

an alkylethyleneoxy unit of the formula

—(T₁)_(d)—(CH₂)_(b)(OCH₂CH₂)_(a)—B₃ or an ester of the formula COOR₂₃;and

U is [Q₁]_(r) ⁻A_(s) ⁺; or Q₂.

R₁₆, R₁₇, R₁₈, R₁₉, R₂₀, R₂₁, R₂₂, R₂₃, B₂, B₃, M, M₁, Q₁, Q₂, A_(s),T₁, X₁, Y₂, Z₂, a, b, c, d, e, r, v and w in the above formulae are asdefined for formulae (1a) and (1b).

Especially preferred as phthalocyanine compound are compounds such asthose commercially available and used in washing agents. Usually, theanionic phthalocyanine compounds are in the form of alkali metal salts,especially sodium salts.

Preferred formulations of the granules contain from 4 to 30% by weight,especially from 5 to 20% by weight, of phthalocyanine compound, based onthe total weight of the granules.

It will be understood that it is also possible to use mixtures of two ormore phthalocyanine compounds instead of a single, homogeneousphthalocyanine compound.

The anionic dispersing agents used are, for example, the commerciallyavailable water-soluble anionic dispersing agents for dyes, pigmentsetc. The following products, especially, come into consideration:condensation products of aromatic sulfonic acids and formaldehyde,condensation products of aromatic sulfonic acids with unsubstituted orchlorinated diphenylene or diphenyl oxides and optionally form-aldehyde,(mono-/di-)alkylnaphthalenesulfonates, sodium salts of polymerisedorganic sulfonic acids, sodium salts of polymerisedalkylnaphthalenesulfonic acids, sodium salts of polymerisedalkylbenzenesulfonic acids, alkylarylsulfonates, sodium salts of alkylpolyglycol ether sulfates, polyalkylated polynuclear arylsulfonates,methylene-linked condensation products of arylsulfonic acids andhydroxyarylsulfonic acids, sodium salt of dialkyl-sulfosuccinic acid,sodium salts of alkyl diglycol ether sulfates, sodium salts ofpoly-naphthalenemethanesulfonates, ligno- or oxyligno-sulfonates orheterocyclic polysulfonic acids.

The dispersing agents may be used individually or in the form of amixture of two or more dispersing agents.

Especially suitable anionic dispersing agents are condensation productsof naphthalene-sulfonic acids with formaldehyde, sodium salts ofpolymerised organic sulfonic acids,(mono-/di-)alkylnaphthalenesulfonates, polyalkylated polynuclear arylsulfonates, sodium salts of polymerised alkylbenzenesulfonic acid,lignosulfonates, oxylignosulfonates and condensation products ofnaphthalenesulfonic acid with a polychloromethyldiphenyl.

Preferably, the granules according to the invention contain from 40 to90% by weight, especially from 50 to 90% by weight, of anionicdispersing agent. In addition to the water-soluble phthalocyaninecompound and the anionic dispersing agent, the granules according to theinvention may comprise a water-soluble organic polymer. Such polymersmay be used individually or in the form of a mixture of two or morepolymers. Preferably, such a polymer is added for the purpose ofimproving the mechanic stability of the granules and/or when, duringlater use of the granules in a washing agent, the phthalocyaninecompound is to be prevented from being dissolved out of the granules bya non-ionic surfactant.

There come into consideration as water-soluble polymers, for example,gelatin, poly-acrylates, polymethacrylates, copolymers of ethyl acetate,methyl methacrylate and methacrylic acid (ammonium salt),polyvinylpyrrolidones, vinylpyrrolidones, vinyl acetates, copolymers ofvinylpyrrolidone with long-chained a-olefins, poly(vinylpyrrolidone/dimethylaminoethyl methacrylates), copolymers ofvinylpyrrolidone/dimethylaminopropyl methacrylamides, copolymers ofvinylpyrrolidonedimethylaminopropyl acrylamides, quaternised copolymersof vinylpyrrolidones and dimethylaminoethyl methacrylates, terpolymersof vinylcaprolactamvinylpyrrolidonedimethylaminoethyl methacrylates,copolymers of vinylpyrrolidone andmethacrylamidopropyl-trimethylammonium chloride, terpolymers ofcaprolactamvinylpyrrolidonedimethylaminoethyl methacrylates, copolymersof styrene and acrylic acid, polycarboxylic acids, polyacrylamides,carboxymethylcellulose, hydroxymethylcellulose, polyvinyl alcohols,polyvinyl acetate, hydrolysed polyvinyl acetate, copolymers of maleicacid with unsaturated hydrocarbons, and mixed polymerisation products ofthe mentioned polymers.

Of those organic polymers, carboxymethylcellulose, polyacrylamides,polyvinyl alcohols, polyvinylpyrrolidones, gelatin, hydrolysed polyvinylacetates, copolymers of vinylpyrrolidone and vinyl acetate, and alsopolyacrylates and polymethacrylates, are especially preferred.

The organic polymers are used in an amount of from 0 to 25% by weight,preferably from 5 to 20% by weight and, especially, from 8 to 18% byweight, based on the total weight of the granules.

The granules according to the invention may comprise further additives,for example wetting agents, water-insoluble or water-soluble dyes orpigments, and also dissolution accelerators and optical brighteners.Such additives are present in an amount of from 0 to 10% by weight,based on the total weight of the granules.

The granules according to the invention are produced, for example, inthe following manner: first of all an aqueous solution of thephthalocyanine dye is prepared, the anionic dispersing agent and, ifdesired, further additives are added thereto, and the mixture isstirred, where appropriate with heating, until a homogeneous solution isobtained. The solids content of the solution should preferably be atleast 30% by weight, especially from 40 to 50% by weight, based on thetotal weight of the solution. The viscosity of the solution ispreferably less than 200 mPas.

The aqueous solution comprising the phthalocyanine dye and the anionicdispersing agent is then subjected to a drying step in which all water,with the exception of a residual amount, is removed, solid particles(granules) simultaneously being formed. Known methods are suitable forproducing the granules from the aqueous solution. In principle, bothcontinuous methods and discontinuous methods are suitable. Continuousmethods are preferred, especially spray-drying and fluidized bedgranulation processes.

Especially suitable are spray-drying processes in which the activeingredient solution is sprayed into a chamber with circulating hot air.The atomisation of the solution is carried out using unitary or binarynozzles or is brought about by the spinning effect of a rapidly rotatingdisc. In order to increase the particle size, the spray-draying processmay be combined with an additional agglomeration of the liquid particleswith solid nuclei in a fluidized bed that forms an integral part of thechamber (so-called fluidized spray dryer). The fine particles (<100 μm)obtained by a conventional spray-drying process may, if necessary afterbeing separated from the exhaust gas flow, be fed without being furthertreated directly into the atomizing cone of the atomiser of the spraydryer as nuclei, for the purpose of agglomeration with the liquiddroplets of the active ingredient.

During the granulation step, the water can rapidly be removed from thesolutions comprising phthalocyanine compound, anionic dispersing agentand possibly organic polymer and further additives, and it is expresslyintended that agglomeration of the droplets forming in the atomisingcone, i.e. the agglomeration of, droplets with solid particles, willtake place.

If necessary, the granules formed in the spray-dryer are removed in acontinuous process, for example by a sieving operation. The fines andthe oversize particles are either recycled directly to the process(without being redissolved) or are dissolved in the liquid activeingredient formulation and subsequently granulated again.

The granules according to the invention are resistant to abrasion, lowin dust, free-flowing and can readily be metered. They are distinguishedin particular by very rapid solubility in water. They are usedespecially in washing agent formulations. They may be added in thedesired concentration of the phthalocyanine compound directly to awashing agent formulation. The present invention relates also to thatuse.

Where the dark appearance of the granules in the washing agent is to besuppressed, this can be achieved, for example, by embedding the granulesin a droplet of a whitish meltable substance (“water-soluble wax”) or,preferably, by encapsulating the granules in a melt consisting, forexample, of a water-soluble wax, as described in EP-B-0 323 407 B1, awhite solid (e.g. titanium dioxide) being added to the melt in order toreinforce the masking effect of the capsule.

The present invention accordingly relates also to washing agentformulations comprising

I) from 5 to 70% A) of an anionic surfactant and/or B) of a non-ionicsurfactant,

II) from 5 to 50% C) of a builder substance,

III) from 1 to 12% D) of a peroxide and, where appropriate, a catalystand

IV) from 0.01 to 1% E) of granules according to the invention,

the percentages in each case being percentages by weight, based on thetotal weight of the washing agent.

Preference is given to washing agent formulations comprising

I) from 5 to 70% A) of an anionic surfactant: and/or B) of a non-ionicsurfactant,

II) from 5 to 40% C) of a builder substance.

III) from 1 to 12% D) of a peroxide and, where appropriate, a catalystand

IV) from 0.01 to 0.5% E) of granules according to the invention,

the percentages in each case being percentages by weight, based on thetotal weight of the washing agent.

The washing agent may be in solid or liquid form, for example in theform of a liquid non-aqueous washing agent containing not more than 5%by weight, preferably from 0 to 1% by weight, of water, and may have asbase a suspension of a builder substance in a non-ionic surfactant, forexample as described in GB-A-2 158 454.

Preferably, however, the washing agent is in the form of a powder orgranules, which can be produced, for example, by first of all preparinga starting powder by spray-drying an aqueous suspension containing allof the components listed above with the exception of components D) andE), and then adding the dry components D) and E) and mixing everythingtogether.

It is also possible to start with an aqueous suspension that containscomponents A) and C), but not component B) or only some of component B).The suspension is spray-dried, then component E) is mixed with componentB) and the mixture is added to the suspension, and subsequentlycomponent D) is admixed dry.

Preferably, the components are mixed with one another in such amountsthat a solid compact washing agent in the form of granules is obtainedthat has a specific weight of at least 500 g/l.

In another preferred embodiment, the production of the washing agent iscarried out in three steps. In the first step a mixture of anionicsurfactant (and, where appropriate, a small amount of non-ionicsurfactant) and builder substance is prepared. In the second step thatmixture is sprayed with the major portion of the non-ionic surfactantand then, in the third step, peroxide, where appropriate catalyst, andthe granules according to the invention are added. That method isusually carried out in a fluidized bed.

In a further preferred embodiment, the individual steps are not carriedout completely separately, so that there is a certain amount of overlapbetween them. Such a method is usually carried out in an extruder, inorder to obtain granules in the form of megapearls.

The anionic surfactant A) may be, for example, a sulfate, sulfonate orcarboxylate surfactant or a mixture of those surfactants.

Preferred sulfates are those having from 12 to 22 carbon atoms in thealkyl radical, where appropriate in combination with alkylethoxysulfates having from 10 to 20 carbon atoms in the alkyl radical.

Preferred sulfonates are, for example, alkylbenzenesulfonates havingfrom 9 to 15 carbon atoms in the alkyl radical and/or alkylnaphthialenesulfonates having from 6 to 16 carbon atoms in the alkylradical in question.

The cation in the anionic surfactant is prefenably an alkali metalcation, especially sodium.

Preferred carboxylates are alkali metal sarcosinates of the formulaR—CO—N(R¹)—CH₂COOM¹, wherein R is alkyl or alkenyl having from 8 to 18carbon atoms in the alkyl or alkenyl radical, R¹ is C₁-C₄alkyl and M¹ isan alkali metal.

The non-ionic surfactant B) may be, for example, a condensation productof from 3 to 8 mols of ethylene oxide with 1 mol of primary alcohol thatcontains from 9 to 15 carbon atoms.

There come into consideration as builder substance C), for example,alkali metal phosphates, especially tripolyphosphates, carbonates orhydrogen carbonates, especially the sodium salts, silicates, aluminumsilicates, polycarboxylates, polycarboxylic acids, organic phosphonates,aminoalkylenepoly(alkylenephosphonates) or mixtures of those compounds.

Especially suitable silicates are sodium salts, of crystalline silicateshaving layered structures of the formula NaHSi_(t)O_(2t+1)·pH₂O orNa₂Si_(t)O_(2t+1)·pH₂O, wherein t is a number from 1.9 to 4 and p is anumber from 0 to 20.

Among the aluminum silicates, preference is given to those obtainablecommercially under the names zeolite A, B, X and HS, and also tomixtures comprising two or more of those components.

Among the polycarboxylates, preference is given topolyhydroxycarboxylates, especially citrates, and acrylates and alsocopolymers thereof with maleic anhydride.

Preferred polycarboxylic acids are nitrilotriacetic acid,ethylenediaminetetraacetic acid and ethylenediamine disuccinate eitherin racemic form or in the enantiomerically pure S,S form.

Phosphonates or aminoalkylenepoly(alkylenephosphonates) that areespecially suitable are alkali metal salts of1-hydroxyethane-1,1-diphosphonic acid, nitrilotris(methylenephosphonicacid), ethylenediaminetetramethylene.phosphonic acid anddiethylenetriaminepentamethylenephosphonic acid.

There come into consideration as the peroxide component D), for example,the organic and inorganic peroxides known in the literature andavailable commercially that bleach textile materials at conventionalwashing temperatures, for example at from 10 to 950° C.

The organic peroxides are, for example, mono- or poly-peroxides,especially organic peracids or salts thereof, such asphthalimidoperoxycaproic acid, peroxybenzoic acid, diperoxydodecanoicdiacid, diperoxynonanoic diacid, diperoxydecanoic diacid,diperoxyphthalic acid or salts thereof.

Preferably, however, inorganic peroxides are used, such as, for example,persulfates, perborates, percarbonates and/or persilicates. It will beunderstood that mixtures of inorganic and/or organic peroxides can alsobe used. The peroxides may be in a variety of crystalline forms and havedifferent water contents, and they may also be used together with otherinorganic or organic compounds in order to improve their storagestability.

The peroxides are added to the washing agent preferably by mixing thecomponents, for example using a screw metering system and/or a fluidizedbed mixer.

The washing agents may comprise, in addition to the combinationaccording to the invention, one or more optical brighteners, for examplefrom the class bis-triazinylaminostilbenedisulfonic acid,bis-triazolylstilbenedisulfonic acid, bis-styrylbiphenyl orbis-benzofuranylbiphenyl, a bis-benzoxalyl derivative,bis-benzimidazolyl derivative or coumarin derivative or a pyrazolinederivative.

The washing agent may also comprise suspending agents for dirt, e.g.sodium carboxymethylcellulose, pH regulators, e.g. alkali metal oralkaline earth metal silicates, foam regulators, e.g. soap, salts forregulating the spray-drying and the granulating properties, e.g. sodiumsulfate, perfumes and, optionally, antistatic agents and softeners,enzymes, such as amylase, bleaches, pigments and/or toning agents. Itwill be understood that such constituents must be stable towards thebleaching agent used.

Further preferred additives to the washing agents according to theinvention are polymers which, during the washing of textiles, preventstaining caused by dyes in the washing liquor which have been releasedfrom the textiles under the washing conditions. Such polymers arepreferably polyvinylpyrrolidones which, where appropriate, have beenmodified by the incorporation of anionic or cationic substituents,especially those having a molecular weight in the range from 5000 to 60000, more especially from 10 000 to 50 000.Such polymers are preferablyused in an amount of from 0.05 to 5% by weight, especially from 0.2 to1.7% by weight, based on the total weight of the washing agent.

In addition, the washing agents according to the invention may alsocomprise so-called perborate activators, such as, for example, TAED orTAGU. Preference is given to TAED, which is preferably used in an amountof from 0.05 to 5% by weight, especially from 0.2 to 1.7% by weight,based on the total weight of the washing agent.

The following Examples serve to illustrate the invention withoutlimiting the invention thereto. Parts and percentages relate to weight,unless specified otherwise.

EXAMPLE 1

725 g of an aqueous solution of a zinc phthalocyanine compound (sodiumsalt of zinc phthalocyanine, containing 3 or 4 sulfo groups) having asolids content of 20% by weight are introduced into a glass beaker. 3010g of an aqueous solution containing 40% by weight of an anionicdispersing agent (condensation product of naphthalenesulfonic acid andformaldehyde) are added to the first solution. Thephthalocyaninedispersing agent mixture having a solids content ofapproximately 34% by weight is homogenised by stirring at 25° C. for 1hour. The solution is then spray-dried in a spray dryer equipped with aunitary nozzle. The exhaust air temperature is 105° C. at a feed airtemperature of 195° C. Free-flowing granules having an average particlesize of 50 μm and a residual water content of 7% are obtained. Thegranules produced in that manner contain 10% zinc phthalocyanine.

EXAMPLES 2 TO 7

Granules having the following compositions are produced according to thesame procedure: the phthalocyanines in Examples 2 to 48 each contain 3or 4 sulfo groups and are in the form of sodium salts.

Anionic Residual Ex. % by dispersing % by moisture in No. Dye weightagent weight the granules 2 aluminium 15 condensation pro- 80 5% byphthalo- duct of formalde- weight cyanine hyde with naphthalene-sulfonicacid 3 zinc 5 sodium salt of 86 9% by phthalo- polymerised alkyl- weightcyanine naphthalenesulfonic acid 4 zinc 20 oxylignosulfonate 76 4% byphthalo- sodium salt weight cyanine 5 aluminium 6 heterocyclic poly- 786% by phthalo- sulfonic acid weight cyanine 6 zinc 9 condensation 82 9%by phthalo- product of weight cyanine formaldehyde with naphthalene-sulfonic acid 7 zinc 10 condensation 56 5% by phthalo- product of weightcyanine formaldehyde with naphthalene- sulfonic acid alkylnaphthalene-29 sulfonic acid sodium salt

EXAMPLE 8

880 g of an aqueous solution of an aluminum phthalocyanine compound(sodium salt of aluminum phthalocyanine, containing 3 or 4 sulfo groups)having a solids content of 25% by weight are introduced into a glassbeaker and diluted with 1460 g of deionised water. The solution isheated to 45° C. and a dry, pulverulent anionic dispersing agent(condensation product of formaldehyde with naphthalenesulfonic acid) isintroduced in portions into the heated solution. Thedispersing-agent-containing phthalocyanine solution is then stirred at45° C. for 2 hours in order that the dispersing agent is completelydissolved.

the finished phthalocyaninedispersing agent solution having a solidscontent of 45% is granulated while still warm in a bench fluidized spraydryer. In the first phase of that granulation procedure, the nuclei areformed in the fluidized bed (T_(feed air)=200° C., T_(bed)=950° C.).Once enough nuclei are present in the fluidized bed for the granulation,the bed temperature is reduced to approximately 50° C. in order toinitiate the granulation process. The granulation of the entirephthalocyanine solution is carried out at a fluidized bed temperature offrom 48 to 51° C. The granules discharged from the granulator have aresidual moisture content of approximately 14% by weight and are thendried to the desired value of 9% by weight in a continuously operatingfluidized bed with air at a temperature of 750° C.

The free-flowing granules have an average particle size of 160 μm andcontain 10% by weight aluminum phthalocyanine compound.

EXAMPLES 9 to 14

Granules having the following compositions are produced according to thesame procedure:

Anionic Residual Ex. % by dispersing % by moisture in No. Dye weightagent weight the granules 9 zinc 14 dialkyl naphthalene- 80 6% byphthalo- sulfonate sodium weight cyanine salt 10 zinc 10 condensation 855% by phthalo- product of formal- weight cyanine dehyde with naph-thalensulfonic acid 11 aluminium 6 naphthalenesulfonic 86 8% by phthalo-acid sodium salt weight cyanine condensed with formaldehyde 12 aluminium12 condensation pro- 82 4% by phthalo- duct of sulfonated weight cyaninenaphthalene with a polychloromethyl- diphenyl mixture 13 aluminium 18dinaphthylmethane- 77 5% by phthalo- sulfonic acid, weight cyaninesodium salt 14 aluminium 14 sodium lignosulfate 36 5% by phthalo-dinaphthylmethane- 45 weight cyanine sulfonic acid

EXAMPLE 15

The preparation of the phthalocyanine solution and the typicalformulations of the phthalocyanine granules correspond to Examples 1 to7. Unlike Example 1, the granulation is carried out in a spray dryer inwhich the fines produced during the process are continuously separatedfrom the waste gas flow and are conveyed directly by a gas flow into theatomizing cone of the nozzle. The resulting granules have the sameproperties as those already described in Example 1. Their averageparticle size is 112 μm, so that they are obtained in a substantiallycoarser particle size than in Example 1. The product from this Examplecontains substantially less fine dust (max. 4.5% of particles<20 μm,compared with 15% by weight in Example 1).

EXAMPLE 16

512 g of an anionic dispersing agent (condensation product offormaldehyde with naphthalenesulfonic acid) and 1000 g of a furtheranionic dispersing agent (methylene-linked condensation product ofarylsulfonic acids and hydroxyarylsulfonic acids) are dissolved insuccession in 1980 g of a 10% aqueous solution of the zincphthalocyanine compound from Example 1, which has been heated to 50° C.The aqueous phthalocyanine formulation is then stirred for 3 hours, inorder that all components are completely dissolved. Some of thephthalocyanine solution is then dried in vacuo for 48 hours and the drymaterial is then ground in a mortar.

The ground product is subsequently introduced into a laboratoryfluidized bed granulator (STREA-1; Aeromatic AG, Bubendorf, Switzerland)as granulation nuclei. The nuclei are fluidized with the hot air(approximately 65° C.) flowing into the granulator through theperforated base. The phthalocyanine solution is then sprayedcontinuously into the fluidized bed using a binary nozzle. Afterapproximately 90 minutes, the granulation (metering in of thephthalocyanine solution) is terminated. Once the granulation isconcluded the granules are dried in the same equipment, with air at atemperature of 80° C., to a residual water content of 5% by weight.

The particles are then discharged and the fines are removed by sieving.The average particle size is 380 μm.

EXAMPLES 17 TO 22

Granules having the following compositions are produced according to thesame procedure as that in Example 16:

Anionic Residual Ex. % by dispersing % by moisture in No. Dye weightagent weight the granules 17 aluminium 6 oxylignosulfonate 84 10% byphthalo- sodium salt weight cyanine 18 zinc 10 condensation pro- 85  5%by phthalo- duct of formalde weight cyanine hyde with naphtha-lenesulfonic acid 19 aluminium 17 alkyl polyglycol 79  4% by phthalo-ether sulfate weight cyanine sodium salt 20 alum- 9 sodium lignosulfate82  9% by inium weight phthalo- cyanine 21 zinc 15 condensation pro- 77 8% by phthalo- duct of sulfonated weight cyanine naphthalene with apolychloromethyl- diphenyl mixture 22 aluminium 10 lignosulfonate 85  5%by phthalo- weight cyanine

EXAMPLE 23

826 g of a pulverulent dispersing agent (condensation product offormaldehyde with naphthalenesulfonic acid) are stirred into anddissolved in 1073 g of an aqueous solution of the zinc phthalocyaninecompound from Example 1 having a solids content of 11% by weight. Theaqueous phthalocyanine solution is stirred for 1 hour in order that thedispersing agent is completely dissolved.

In a glass beaker, 177 g of a water-soluble polyacrylamide (MW=200 000)are dissolved in 700 g of deionised water by heating the solution to amaximum of 50° C. Once the polymer has dissolved completely, thephthalocyanine solution is added with stirring. The preparation isstirred for one hour and then filtered through a filter having a poresize of 0.5 μm.

The filtrate is granulated in a spray dryer in which the fines producedduring the process are continuously separated from the exhaust gas flowand conveyed directly by a gas flow into the spray cone of the nozzle.The granules are free-flowing and have an average particle size of 105μm. The fines (particle size <20 μm) content is 6.2%. The fraction <50μm is removed by an air-jet sieve from the particles of the desiredsize.

The granules are completely soluble in water within a period of lessthan 2 minutes. When stored in a non-ionic surfactant, no dissolving outof the phthalocyanine compound is detected even after several days.

EXAMPLES 24 TO 34

The formulations listed in the following Table are produced analogouslyto Example 23 and, after spray-drying, result in granules having thesame properties in terms of particle size, solubility in water andnon-ionic surfactants as the granules according to Example 23.

Residual Ex. % by Anionic dispersing % by Water-soluble % by moisture inNo. Dye weight agent weight polymer weight the granules 24 aluminium 7oxylignosulfonate 73 low-viscosity 12 8% by phthalocyanine sodium saltsodium carboxy- weight methylcellulose 25 zinc phthalo- 10 condensationproduct of 70 water-soluble 15 5% by cyanine formaldehyde with naph-polyacrylamide, weight thalenesulfonic acid MW = 200 000 26 aluminium 12alkyl polyglycol ether 71 polyvinyl 13 4% by phthalocyanine sulfatesodium salt alcohol weight 27 aluminium 15 sodium ligno- 58 polyvinyl-18 9% by phthalocyanine sulfonate pyrrolidone weight 28 zinc phthalo- 12condensation product of 72 hydrolysed 10 6% by cyanine sulfonatednaphthalene polyvinyl acetate weight with a polychloromethyl- diphenylmixture 29 aluminium 10 sodium ligno- 78 copolymer of vinyl- 7 5% byphthalocyanine sulfonate pyrrolidone with weight vinyl acetate 30 zincphthalo- 5 condensation product of 78 gelatin 10 7% by cyaninesulfonated naphthalene weight with a polychloromethyl- diphenyl mixture31 zinc phthalo- 15 sodium ligno- 65 polyvinyl alcohol 14 6% by cyaninesulfonate 15 000 weight 32 zinc phthalo- 10 condensation product of 70ammonium salt of 14 6% by cyanine formaldehyde with naph- a copolymer ofweight thalenesulfonic acid ethyl acrylate, methyl meth- acrylate andmeth- acrylic acid 33 aluminium 11 alkyl polyglycol ether 75 5% byphthalocyanine sulfate sodium salt weight 34 zinc phthalo- 5condensation product of 78 ammonium salt of 10 7% by cyanine sulfonatednaphthalene a copolymer of weight with a polychloromethyl- ethylacrylate, diphenyl mixture methyl methacryl- ate and methacrylic acid

EXAMPLE 35 TO 53

The formulations listed in the following Table are obtained by first ofall preparing aqueous solutions of the components and then granulatingthose solutions in a fluidized spray dryer.

As already described in Example 8, in the first phase of the granulationprocedure the equipment is operated as a spray dryer in order to producein the fluidized bed the nuclei necessary for the granulation(T_(feed air)=210° C., T_(bed)=115° C). Once enough nuclei are presentin the fluidized bed for the granulation, the bed temperature is reducedto approximately 65° C. in order to initiate the granulation process.The granulation of the phthalocyanine solution is carried out at afluidized bed temperature of from 60 to 68° C. The granules dischargedfrom the granulator have a residual moisture content of approximately12% by weight and are then dried to the formulation-specific desiredvalue (see following Table) in a continuously operating fluidized bedinto which air at a temperature of 85° C. is fed. Irrespective of theformulation in question, the granules are free-flowing, are rapidlydissolved in water and are not visibly soluble in non-ionic surfactantsfor a period of days.

Residual Ex. Anionic dispersing Water-soluble moisture in No. Dye % byweight agent % by weight polymer % by weight the granules 35 zinophthalo- 10 oxylignosulfonate 75 low-viscosity carb- 10 5% by cyaninesodium salt oxymethylcellulose weight 36 aluminium phthalo-  7condensation product 71 water-soluble 15 7% by cyanine of formaldehydewith polyacrylamide, weight naphthalenesulfonic MW = 200 000 acid 37zinc phthalo-  8 dinaphthylmethane- 74 sodium polyacrylate 13 5% bycyanine sulfonic acid sodium weight salt 38 zinc phthalo- 11dinaphthylmethane- 73 sodium polymeth- 10 6% by cyanine sulfonic acidacrylate weight sodium salt 39 zinc phthalo- 10 condensation product 69polyvinyl 12 9% by cyanine of formaldehyde with alcohol 15 000 weightnaphthalene- sulfonic acid 40 aluminium phthalo- 12 dialkylsulfosuccinic75 polyvinyl alcohol  9 4% by cyanine acid sodium salt weight 41aluminium phthalo- 15 heterocyclic poly- 62 polyvinyl- 14 9% by cyaninesulfonic acid pyrrolidone weight 42 zinc phthalo-  9 condensationproduct 53 hydrolysed polyvinyl 12 6% by cyanine of formaldehyde withacetate weight naphthalene- sulfonic acid condensation product 20 ofsulfonated naphthalene with a polychloromethyl- diphenyl mixture 43aluminium  8 sodium ligno- 39 copolymer of  9 4% by phthalocyaninesulfonate vinylpyrrolidone with weight dinaphthylmeth- 40 vinyl acetateanesulfonic acid sodium salt 44 zinc phthalo- 10 condensation product 76gelatin  8 6% by cyanine of sulfonated weight naphthalene with apolychloromethyl- diphenyl mixture 45 aluminium phthalo- 15dinaphthylmethane- 61 sodium polyacrylate 15 9% by cyanine sulfonic acidweight 46 aluminium phthalo-  6 dinaphthylmethane- 79 sodium poly- 10 5%by cyanine sulfonic acid, methacrylate weight sodium salt 47 zincphthalocyanine 15 condensation product 43 polyvinyl 10 7% by offormaldehyde with alcohol 15 000 weight naphthalenesulfonic acid sodiumligno- 25 sulfonate 48 zinc phthalo- 11 alkylnaphthalene- 66 sodium saltof a copoly- 15 8% by cyanine sulfonic acid sodium mer of maleic acidand weight salt an unsaturated hydrocarbon 49 aluminium phthalo- 10dinaphthylmethane- 75 copolymer of polyvinyl 10 5% by cyanine sulfonicacid, alcohol and polyvinyl weight sodium salt acetate 50 zinc phthalo-10 dinaphthylmethane- 48 polycaprolactone 10 8% by cyanine sulfonicacid, weight sodium salt condensation product 24 of sulfonatednaphthalene with a polychloromethyl- diphenyl mixture 51 zinc phthalo-10 condensation product 70 water-soluble 15 5% by cyanine offormaldehyde with polyacrylamide, weight naphthalenesulfonic MW = 200000 acid 52 zinc phthalo- 12 alkylnaphthalene- 66 ammonium salt of a 148% by cyanine sulfonic acid copolymer of ethyl weight sodium saltacrylate, methyl methacrylate and methacrylic acid 53 zinc phthalo-  7dinaphthylmethane- 77 ammonium salt of a  8 8% by cyanine sulfonic acid,copolymer of ethyl weight sodium salt acrylate, methyl methacrylate andmethacrylic acid

EXAMPLE 54

The formulations listed in Examples 45 to 51 are granulated in afluidized bed granulator (STREA-1, Aeromatic AG) instead of in thefluidized spray dryer. For that purpose, as explained in Example 16 someof the phthalocyanine solution is dried and ground separately and usedas nuclei in the granulating procedure.

The granules obtained from the fluidized bed granulation have an averageparticle size of from 250 to 480 μm. The average particle size varieswithin that range according to the composition of the formulation.

What is claimed is:
 1. Water-soluble granules of a phthalocyaninecompound comprising a) from 2 to 50% by weight of a water-solublephthalocyanine compound, b) from 40 to 90% by weight of an anionicdispersing agent, c) from 5 to 20% by weight of a water-soluble organicpolymer, d) from 0 to 10% by weight of further additives selected fromwetting agents, water-insoluble or water-soluble dyes or pigments,dissolution accelerators and optical brighteners and e) from 3 to 15% byweight of water, based on the total weight of the granules.
 2. Granulesaccording to claim 1 comprising from 4 to 30% by weight ofphthalocyanine compound.
 3. Granules according to claim 2 comprisingfrom 5 to 20% by weight of phthalocyanine compound.
 4. Granulesaccording to claim 1 comprising from 50 to 90% by weight of anionicdispersing agent.
 5. Granules according to claim 1 comprising from 8 to18% by weight of organic polymer.
 6. Granules according to claim 1comprising as phthalocyanine compound a water-soluble Zn, Fe(II), Ca,Mg, Na, K, Al, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(III), Zr(IV),In(III), Sn(IV) or Hf(VI) phthalocyanine compound.
 7. Granules accordingto claim 6, comprising a phthalocyanine compound of formula[Me]_(q)—[PCQ₁]_(r) ⁻A_(s) ⁻  (1a) or [Me_(q)PCQ₂]_(r)  (1b)wherein PC is the phthalocyanine ring system; Me is Zn, Fe(II), Ca, Mg,Na, K, Al—Z₁, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(III), Zr(IV),In(III), Sn(IV) or Hf(VI); Z₁ is a halide, sulfate, nitrate, acetate orhydroxy ion; q is 0, 1 or 2; r is from 1 to 4; Q₁ is a sulfo or carboxylgroup; or a radical of the formula —SO₂X₂—R₆—X₃ ⁺; —O—R₆—X₃ ⁺; or—(CH₂)_(t)—Y₁ ⁺; wherein R₆ is branched or unbranched C₁-C₈alkylene; or1,3- or 1,4-phenylene; X₂ is —NH—; or —N—C₁-C₅alkyl-; X₃ ⁺ is a group ofthe formula

and, in the case where R₆=C₁-C₈alkylene, may also be a group of theformula

Y₁ ⁺ is a group of the formula

and t is 0 or 1; and in the above formulae R₇ and R₈ are eachindependently of the other C₁-C₆alkyl; R₉ is C₁-C₆alkyl;C₅-C₇cycloalkyl; or NR₁₁R₁₂; R₁₀ and R₁₁ are each independently of theother C₁-C₅alkyl; R₁₂ and R₁₃ are each independently of the otherhydrogen or C₁-C₅alkyl; R₁₄ and R₁₅ are each independently of the otherunsubstituted C₁-C₆alkyl or C₁-C₆alkyl substituted by hydroxy, cyano,carboxy, C₁-C₆alkoxycarbonyl, C₁-C₆alkoxy, phenyl, naphthyl or bypyridyl; u is from 1 to 6; A₁ is the balance of an aromatic 5- to7-membered nitrogen heterocycle which may contain one or two furthernitrogen atoms as ring members, and B₁ is the balance of a saturated 5-to 7-membered nitrogen heterocycle which may contain 1 or 2 furthernitrogen, oxygen and/or sulfur atoms as ring members; Q₂ is hydroxy;C₁-C₂₂alkyl; branched C₄-C₂₂alkyl; C₂-C₂₂alkenyl; branched C₄-C₂₂alkenylor a mixture thereof; C₁-C₂₂alkoxy; a sulfo or carboxyl radical; aradical of the formula

a branched alkoxy radical of the formula

or

an alkylethyleneoxy unit of the formula—(T₁)_(d)—(CH₂)_(b)(OCH₂CH₂)_(a)—B₃ or an ester of the formula COOR₂₃,in which formulae B₂ is hydrogen; hydroxy; C₁-C₃₀alkyl; C₁-C₃₀alkoxy;—CO₂H; —CH₂COOH; SO₃ ⁻M₁ ⁺; —OSO₃ ⁻M₁ ⁺; —PO₃ ²; M₁; —OPO₃ ²⁻M₁; or amixture thereof; B₃ is hydrogen; hydroxy; —COOH; —SO₃ ⁻M₁ ³⁰ ; —OSO₃ ⁻M₁⁺; or C₁-C₆alkoxy; M₁ is a water-soluble cation; T₁ is —O—; or —NH—; X₁and X₄ are each independently of the other —O—; —NH—; or —N—C₁-C₅alkyl;R₁₆ and R₁₇ are each independently of the other hydrogen, a sulfo groupor a salt thereof, a carboxyl group or a salt thereof, or a hydroxylgroup, at least one of the radicals R₁₆ and R₁₇ being a sulfo orcarboxyl group or a salt thereof, Y₂ is —O—, —S—, —NH—or —N—C₁-C₅alkyl;R₁₈ and R₁₉ are each independently of the other hydrogen, C₁-C₆alkyl,hydroxy-C₁-C₆alkyl, cyano-C₁-C₆alkyl, sulfo-C₁-C₆alkyl, carboxy orhalo-C₁-C₆alkyl; unsubstituted phenyl; or phenyl substituted by halogen,C₁-C₄alkyl or C₁-C₄alkoxy, sulfo or by carboxy; or R₁₈ and R₁₉, togetherwith the nitrogen atom to which they are bonded, form a saturated 5- or6-membered heterocyclic ring that may in addition contain a furthernitrogen atom or an oxygen atom as ring member; R₂₀ and R₂₁ are eachindependently of the other a C₁-C₆alkyl or aryl-C₁-C₆alkyl radical; R₂₂is hydrogen; unsubstituted C₁-C₆alkyl; or C₁-C₆alkyl substituted byhalogen, hydroxy, cyano, phenyl, carboxy, C₁-C₆alkoxycarbonyl or byC₁-C₆alkoxy; R₂₃ is C₁-C₂₂alkyl, branched C₄-C₂₂alkyl, C₁-C₂₂alkenyl orbranched C₄-C₂₂alkenyl; C₃-C₂₂glycol; C₁-C₂₂alkoxy; branchedC₄-C₂₂alkoxy; or a mixture thereof; M is hydrogen; or an alkali metalion or ammonium ion; Z₂ is a chlorine, bromine, alkyl sulfate or aralkylsulfate ion; a is 0 or 1; b is from 0 to 6; c is from 0 to 100; d is 0,or 1; e is from 0 to 22; v is an integer from 2 to 12; w is 0 or 1; andA is an organic or inorganic anion, and s in the case of monovalentanions A⁻ is equal to r and in the case of polyvalent anions is ≦r, itbeing necessary for A_(s) ⁻ to balance the positive charge; and whenr≠1, the radicals Q₁ may be identical or different, and wherein thephthalocyanine ring system may also comprise further solubilisinggroups.
 8. Granules according to claim 7 comprising a phthalocyaninecompound of formula

wherein Me, q, PC, X₂, X₃ and R₆ are as defined for formula (1a); M ishydrogen, or an alkali metal, ammonium or amine salt ion; and the sum ofthe numbers r₁ and r₂ is from 1 to 4, and A_(s) ⁻ exactly balances thepositive charge of the remainder of the molecule, or of formula[Me]_(q)—[PC]—[SO₂NHR₆′—X₃′⁺A′⁻]_(r)  (3) wherein Me, q and PC are asdefined for formula (1a); R₆′ is C₂-C₆alkylene; r₁ is a number from 1 to4; X₃′ is a group of the formula

in which formulae R₇ and R₈ are each independently of the otherunsubstituted C₁-C₄alkyl or C₁-C₄alkyl substituted by hydroxy, cyano,halogen or by phenyl; R₉ is R₇; cyclohexyl or amino; R₁₁ is C₁-C₄alkyl;R₂₁ is C₁-C₄alkyl; C₁-C₄alkoxy; halogen, carboxy, C₁-C₄alkoxycarbonyl orhydroxy; and A′ is a halide, alkyl sulfate or aryl sulfate ion; whereinthe radicals —SO₂NHR′₆—X₃′⁺A⁻ may be identical or different.
 9. Granulesaccording to claim 8 comprising a phthalocyanine compound of formula[Me_(q)PCSO₃—Y₃′]_(r)  (4) wherein PC is the phthalocyanine ringsystem; Me is Zn, Fe(II), Ca, Mg, Na, K, Al—Z₁, Si(IV), P(V), Ti(IV),Ge(IV), Cr(VI), Ga(III), Zr(IV), In(III), Sn(IV) or Hf(VI); Z₁ is ahalide, sulfate, nitrate, acetate or hydroxy ion; q is 1; or 2; Y₃′ ishydrogen, an alkali metal ion or an ammonium ion; and r is any numberfrom 1 to
 4. 10. Granules according to claim 9 comprising aphthalocyanine compound of formula (4) wherein Me is Zn or Al—Z₁; and Z₁is a halide, sulfate, nitrate, acetate or hydroxy ion.
 11. Granulesaccording to claim 1 comprising as anionic dispersing agent acondensation product from the following group: condensation products ofaromatic sulfonic acids and formaldehyde, condensation products ofaromatic sulfonic acids with unsubstituted or chlorinated diphenylene ordiphenyl oxides and optionally formaldehyde,(mono-/di-)-alkylnaphthalenesulfonates, sodium salts of polymerisedorganic sulfonic acids, sodium salts of polymerisedalkylnaphthalenesulfonic acids, sodium salts of polymerisedalkylbenzenesulfonic acids, alkylarylsulfonates, sodium salts of alkylpolyglycol ether sulfates, polyalkylated polynuclear arylsulfonates,methylene-linked condensation products of arylsulfonic acids andhydroxyarylsulfonic acids, sodium salt of dialkylsulfosuccinic acid,sodium salts of alkyl diglycol ether sulfates, sodium salts ofpolynaphthalenemethanesulfonates, ligno- or oxyligno-sulfonates orheterocyclic polysulfonic acids.
 12. Granules according to claim 11comprising as anionic dispersing agent a condensation product from thefollowing group: condensation products of naphthalenesulfonic acids withformaldehyde, sodium salts of polymerised organic sulfonic acids,(mono-/di-)alkylnaphthalenesulfonates, polyalkylated polynucleararylsulfonates, sodium salts of polymerised alkylbenzenesulfonic acid,lignosulfonates, oxylignosulfonates and condensation products ofnaphthalenesulfonic acid with a polychloromethyldiphenyl.
 13. Granulesaccording to claim 1 comprising as water-soluble polymer a compound fromthe following group: gelatin, polyacrylates, polymethacrylates,polyvinylpyrrolidones, vinylpyrrolidones, vinyl acetates, copolymers ofvinylpyrrolidone with long-chained α-olefins,poly(vinylpyrrolidonedimethylaminoethyl methacrylates), copolymers ofvinylpyrrolidone/dimethylaminopropyl methacrylamides, copolymers ofvinylpyrrolidone/dimethylaminopropyl acrylamides, quaternised copolymersof vinylpyrrolidones and dimethylaminoethyl methacrylates, terpolymersof vinylcaprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylates,copolymers of vinylpyrrolidone andmethacrylamidopropyl-trimethylammonium chloride, terpolyrners ofcaprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylates,copolymers of styrene and acrylic acid, polycarboxylic acids,polyacrylamides, carboxymethylcellulose, hydroxymethylcellulose,polyvinyl alcohols, polyvinyl acetate, hydrolysed polyvinyl acetate,copolymers of maleic acid with unsaturated hydrocarbons, and mixedpolymerisation products of the mentioned polymers.
 14. Granulesaccording to claim 13 comprising as water-soluble polymer a compoundfrom the following group: carboxymethylcellulose, polyacrylamides,polyvinyl alcohols, polyvinylpyrrolidones, gelatin, hydrolysed polyvinylacetates, copolymers of vinylpyrrolidone and vinyl acetate, and alsopolyacrylates and polymethacrylates.
 15. A method of producing thegranules according to claim 1, wherein first of all an aqueous solutionof the phthalocyanine dye is prepared, the anionic dispersing agent and,if desired, further additives are added thereto, the mixture is stirreduntil a homogeneous solution is obtained, and the aqueous solution isthen subjected to a drying step in which all water, with the exceptionof a residual amount, is removed, solid particles (granules)simultaneously being formed.
 16. A method according to claim 15, whereinthe removal of water is effected by spray-drying.
 17. A method accordingto claim 16, wherein the removal of water is effected by spray-dryingwith direct return of the fine particles of solid to the spraying zone.18. A method according to claim 15, wherein the removal of water iscarried out in a fluidized bed dryer.
 19. A method according to claim15, wherein the removal of water is carried out in a fluidized bedgranulator.
 20. A washing agent formulation comprising I) from 5 to 70%A) of an anionic surfactant and/or B) of a non-ionic surfactant, II)from 5 to 50% C) of a builder substance, III) from 1 to 12% D) of aperoxide and, where appropriate, a catalyst and IV) from 0.01 to 1% E)of granules according to claim 1, the percentages in each case beingpercentages by weight, based on the total weight of the washing agent.21. Granules according to claim 10 comprising a phthalocyanine compoundof formula

wherein PC is the phthalocyanine ring system; Me is Zn, Fe(II), Ca, Mg,Na, K, Al—Z₁, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(III), Zr(IV),In(III), Sn(IV) or Hf(VI); q is 1 or 2; R₁₇′ and R₁₈′ are eachindependently of the other hydrogen, phenyl, sulfophenyl, carboxyphenyl,C₁-C₆alkyl, hydroxy-C₁-C₆alkyl, cyano-C₁-C₆alkyl, sulfo-C₁-C₆alkyl,carboxy-C₁-C₆alkyl or halo-C₁-C₆alkyl or, together with the nitrogenatom, form a morpholine ring; q′ is an integer from 2 to 6; and r is anumber from 1 to 4; wherein, when r>1, the radicals

present in the molecule may be identical or different.
 22. Granulesaccording to claim 8 comprising a phthalocyanine compound of formula

wherein PC is the phthalocyanine ring system; Me is Zn, Fe(II), Ca, Mg,Na, K, Al—Z₁, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(III), Zr(IV),In(III), Sn(IV) or Hf(VI); q is 1; or 2; Y′₃ is hydrogen, an alkalimetal ion or an ammonium ion; q′ is an integer from 2 to 6; R₁₇′ andR₁₈′ are each independently of the other hydrogen, phenyl, sulfophenyl,carboxyphenyl, C₁-C₆alkyl, hydroxy-C₁-C₆alkyl, cyano-C₁-C₆alkyl,sulfo-C₁-C₆alkyl, carboxy-C₁-C₆alkyl or halo-C₁-C₆alkyl or, togetherwith the nitrogen atom, form a morpholine ring, m′ is 0 or 1; and r andr₁ are each independently of the other any number from 0.5 to 3.5, thesum r+r₁ being a minimum of 1 and a maximum of
 4. 23. Granules accordingto claim 8 comprising a phthalocyanine compound of formula

wherein R₂₄ is hydroxy; C₁-C₂₂alkyl; branched C₄-C₂₂alkyl;C₁-C₂₂alkenyl; branched C₄-C₂₂alkenyl or a mixture thereof;C₁-C₂₂alkoxy; a sulfo or carboxyl radical; a radical of the formula

branched alkoxy radical of the formula

or

an alkylethyleneoxy unit of the formula—(T₁)_(d)—(CH₂)_(b)(OCH₂CH₂)_(a)—B₃ or an ester of the formula COOR₂₃;and U is [Q₁]_(r) ⁺A_(s) ⁻; or Q₂, Q₁ is a sulfo or carboxyl group; or aradical of the formula —SO₂X₂—R₆—X₃ ⁺; —O—R₆—X₃ ⁺; or —(CH₂)_(t)—Y₁ ⁺;Q₂ is hydroxy; C₁-C₂₂alkyl; branched C₄-C₂₂alkyl; C₂-C₂₂alkenyl;branched C₄-C₂₂alkenyl or a mixture thereof; C₁-C₂₂alkoxy; a sulfo orcarboxyl radical; a radical of the formula

a branched alkoxy radical of the formula

an alkylethyleneoxy unit of the formula—(T₁)_(d)—(CH₂)_(b)(OCH₂CH₂)_(a)—B₃ or an ester of the formula COOR₂₃,in which formulae B₂ is hydrogen; hydroxy; C₁-C₃₀alkyl; C₁-C₃₀alkoxy;—CO₂H; —CH₂COOH; SO₃ ⁻M₁ ⁺; —OSO₃ ⁻M₁ ⁺; —PO₃ ²⁻; M₁; —OPO₃ ²⁻M₁ ⁺; or amixture thereof; B₃ is hydrogen; hydroxy; —COOH; —SO₃ ⁻M₁ ⁺; orC₁-C₆alkoxy; —OSO₃ ⁻M₁ ⁺; or C₁-C₆alkoxy; M₁ is a water-soluble cation;T₁ is —O—; or —NH—; X₁ and X₄ are each independently of the other —O—;—NH—; or —N—C₁-C₅alkyl; R₁₆ and R₁₇ are each independently of the otherhydrogen, a sulfo group or a salt thereof, a carboxyl group or a saltthereof, or a hydroxyl group, at least one of the radicals R₁₆ and R₁₇being a sulfo or carboxyl group or a salt thereof, Y₂ is —O—, —S—, —NH—or —N—C₁-C₅alkyl; R₁₈ and R₁₉ are each independently of the otherhydrogen, C₁-C₆alkyl, hydroxy-C₁-C₆alkyl, cyano-C₁-C₆alkyl,sulfo-C₁-C₆alkyl, carboxy or halo-C₁-C₆alkyl; unsubstituted phenyl; orphenly substituted by halogen, C₁-C₄alkyl or C₁-C₄alkoxy, sulfo or bycarboxy; or R₁₈ and R₁₉, together with the nitrogen atom to which theyare bonded, form a saturated 5- or 6-membered heterocyclic ring that mayin addition contain a further nitrogen atom or an oxygen atom as ringmember; R₂₀ and R₂₁ are each independently of the other a C₁-C₆alkyl oraryl-C₁-C₆alkyl radical; R₂₂ is hydrogen; unsubstituted C₁-C₆alkyl; orC₁-C₆alkyl substituted by halogen, hydroxy, cyano, phenyl, carboxy,C₁-C₆alkoxycarbonyl or by C₁-C₆alkoxy; R₂₃ is C₁-C₂₂alkyl, branchedC₄-C₂₂alkyl, C₁-C₂₂alkenyl or branched C₄-C₂₂alkenyl; C₃-C₂₂glycol;C₁-C₂₂alkoxy; branched C₄-C₂₂alkoxy; or a mixture thereof; M ishydrogen; or an alkali metal ion or ammonium ion; Z₂ is a chlorine,bromine, alkyl sulfate or aralkyl sulfate ion; a is 0 or 1; b is from 0to 6; c is from 0 to 100; d is 0; or 1; e is from 0 to 22; r is from 1to 4; v is an integer from 2 to 12, and w is 0 or 1; and A is an organicor inorganic anion, and s in the case of monovalent anions A⁻ is equalto r and in the case of polyvalent anions is ≦r, it being necessary forA_(s) ⁻ to balance the positive charge; and when r≠1, the radicals Q₁may be identical or different.